Processes for the synthesis of several new carbene compounds of ruthenium and osmium are provided. These novel complexes function as stable, well-defined catalysts for the metathesis polymerization of cyclic olefins.
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1. In the process of metathesis polymerization of cyclic olefins, the improvement comprising carrying out the polymerization in the presence of a catalyst of the formula ##STR35## in the presence of a solvent, wherein: M is Os or Ru;
R and R1 are independently selected from hydrogen; C1 -C20 alkyl, C2 -C20 alkenyl, C2 -C20 alkynyl, C2 -C20 alkoxycarbonyl, aryl, C1 -C20 carboxylate, C1 -C20 alkoxy, C2 -C20 alkenyloxy, C2 -C20 alkynyloxy or aryloxy; each optionally substituted with C1 -C5 alkyl, halogen, C1 -C6 alkoxy or with a phenyl group substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy; X and X1 are independently selected from an anionic ligand; and L and L1 are independently selected from neutral electron donor.
2. In the process of
3. A process according to
4. A process according to
5. A process according to
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This is a divisional of application Ser. No. 07/863,606, filed Apr. 3, 1992, pending.
This invention relates to new ruthenium and osmium metal carbene complex compounds and their utility in an improved catalytic process for olefin metathesis polymerization.
During the past two decades, research efforts have enabled an in depth understanding of the olefin metathesis reaction as catalyzed by early transition metal complexes. In contrast, the nature of the intermediates and the reaction mechanism for Group VIII transition metal catalysts has remained elusive. In particular, the oxidation states and ligation of the ruthenium and osmium metathesis intermediates are not known. Furthermore, the discrete ruthenium and osmium carbene complexes isolated to date do not exhibit metathesis activity.
Many ruthenium and osmium metal carbenes have been reported in the literature (for example, see Burrell, A. K., Clark, G. R., Rickard, C. E. F., Roper, W. R., Wright, A. H., J. Chem. Soc., Dalton Trans., 1991, Issue 1, pp. 609-614).
The present invention involves a reaction of a ruthenium or osmium compound with either a cyclopropene or a phosphorane to produce well-defined carbene compounds which can be called carbene complexes and which can catalyze the polymerization of cyclic olefin via ring-opening metathesis.
The carbene compounds of the present invention are the only Ru and Os carbene complexes known to date in which the metal is formally in the +2 oxidation state, has an electron count of 16, and is pentacoordinate. The compounds claimed herein are active catalysts for ring-opening metathesis polymerization ("ROMP"). Most metathesis catalysts presently known are poisoned by functional groups and are, therefore, incapable of catalyzing metathesis polymerization reactions in protic or aqueous solvent systems.
Thus, the present invention pertains to compounds of the formula ##STR1## wherein: M is Os or Ru;
R and R1 are independently selected from hydrogen; C2 -C20 alkenyl, C2 -C20 alkynyl, C1 -C20 alkyl, aryl, C1 -C20 carboxylate, C1 -C20 alkoxy, C2 -C20 alkenyloxy, C2 -C20 alkynyloxy, aryloxy, C2 -C20 alkoxycarbonyl, C1 -C20 alkylthio, C1 -C20 alkylsulfonyl or C1 -C20 alkylsulfinyl; each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy;
X and X1 are independently selected from any anionic ligand; and
L and L1 are independently selected from any neutral electron donor.
In one embodiment of these compounds, they can be in the form wherein 2, 3, or 4 of the moieties X, X1, L, and L1 can be taken together to form a chelating multidentate ligand. In one aspect of this embodiment, X, L, and L1 can be taken together to form a cyclopentadienyl, indenyl, or fluorenyl moiety.
The present invention also pertains to a method of preparing the aforementioned ruthenium and osmium compounds comprising reacting a compound of the formula (XX1 MLn L1m)p, in the presence of solvent, with a cyclopropene of the formula ##STR2## wherein: M, X, X1, L, and L1 have the same meaning as indicated above;
n and m are independently 0-4, provided n+m=2, 3 or 4;
p is an integer equal to or greater than 1; and
R2 and R3 are independently selected from hydrogen; C1 -C18 alkyl, C2 -C18 alkenyl, C2 -C18 alkynyl, C2 -C18 alkoxycarbonyl, aryl, C1 -C18 carboxylate, C1 -C18 alkenyloxy, C2 -C18 alkynyloxy, C1 -C18 alkoxy, aryloxy, C1 -C18 alkylthio, C1 -C18 alkylsulfonyl or C1 -C18 alkylsulfinyl; each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy.
In one embodiment of the process, X, L, and L1 are taken together to form a moiety selected from the group consisting of cyclopentadienyl, indenyl or fluorenyl, each optionally substituted with hydrogen; C2 -C20 alkenyl, C2 -C20 alkynyl, C1 -C20 alkyl, aryl, C1 -C20 carboxylate, C1 -C20 alkoxy, C2 -C20 alkenyloxy, C2 -C20 alkynyloxy, aryloxy, C2 -C20 alkoxycarbonyl, C1 -C20 alkylthio, C1 -C20 alkylsulfonyl, C1 -C20 alkylsulfinyl; each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy.
A still further method of preparing the compounds of this invention comprises reacting compound of the formula (XX1 MLn L1m)p in the presence of solvent with phosphorane of the formula ##STR3## wherein: M, X, X1, L, L1, n, m, p, R, and R1 have the same meaning as indicated above; and
R4, R5 and R6 are independently selected from aryl, C1 -C6 alkyl, C1 -C6 alkoxy or phenoxy, each optionally substituted with halogen, C1 -C3 alkyl, C1 -C3 alkoxy, or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy.
Another embodiment of the invention comprises preparing compounds of Formulae II and III ##STR4## from compound of Formula I ##STR5## comprising reacting said compound of Formula I, in the presence of solvent, with compound of the formula M1 Y wherein:
M, R, R1 X, X1 L, and L1 have the same meaning as indicated above, and wherein:
(1) M1 is Li, Na or K, and Y is C1 -C10 alkoxide or arylalkoxide each optionally substituted with C1 -C10 alkyl or halogen, diaryloxide; or
(2) M1 is Na or Ag, and Y is ClO4, PF6, BF4, SbF6, halogen, B(aryl)4, C1 -C10 alkyl sulfonate or aryl sulfonate.
Another embodiment of the present invention is a method of preparing compounds of structures of Formulae IV and V ##STR6## from compound of Formula I ##STR7## comprising reacting said compound I, in the presence of solvent, with L2 wherein:
M, R, R1 X, and X1 have the same meaning as indicated above; and
L, L1, and L2 are independently selected from any neutral electron donor.
The compounds of Formulae II, III, IV, and V are species of, i.e., fall within, the scope of compounds of Formula I. In other words, certain compounds of Formula I are used to form by ligand exchange other compounds of Formula I. In this case, X and X1 in Formula I are other than the Y in Formulae II and III that replaces X. Similarly, L and L1 in Formula I are other than the L2 in Formulae IV and V. If any 2, 3, or 4 of X, X1, L, and L1 form a multidentate ligand of Formula I, only the remaining ligand moieties would be available for ligand replacement.
Still another embodiment of the present invention involves the use of compound I as a catalyst for polymerizing cyclic olefin. More specifically, this embodiment comprises metathesis polymerization of a polymerizable cyclic olefin in the presence of catalyst of the formula ##STR8## in the presence of solvent, wherein: M, R, R1 X X1 L and L1 have the same meaning as indicated above.
The reference above to X, X1, L, and L1 having the same meaning as indicated above refers to these moieties individually and taken together to form a multidentate ligand as described above.
The ruthenium and osmium metal complexes of the present invention are useful as catalysts in ring-opening metathesis polymerization, particularly in the living polymerization of strained cyclic olefins. Although all the criteria for a living polymer have not been completely established, the term living is used in the sense that the propagating moiety is stable and will continue to polymerize additional aliquots of monomer for a period after the original amount of monomer has been consumed. Aspects of this invention include the metal complex compounds, methods for their preparation, as well as their use as catalysts in the ROMP reaction. Uses for the resultant polymer are well documented in the book, Olefin Metathesis, by K. J. Ivin, Academic Press, Harcourt Brace Jovanovich Publishers (1983).
The intermediate compounds (XX1 MLn L1m)p are either available commercially or can be prepared by standard known methods.
The phosphorane and cyclopropene reactants used in the present invention may be prepared in accordance with the following respective references. Schmidbaur, H. et al., Phosphorus and Sulfur, Vol. 18, pp. 167-170 (1983); Carter, F. L., Frampton, V. L., Chemical Reviews, Vol. 64, No. 5 (1964).
In the compounds of Formula I:
alkyl can include methyl, ethyl, n-propyl, i-propyl, or the several butyl, pentyl or hexyl isomers;
alkenyl can include 1-propenyl, 2-propenyl; 3-propenyl and the different butenyl, pentenyl and hexenyl isomers, 1,3-hexadienyl and 2, 4,6-heptatrienyl, and cycloalkenyl;
alkenyloxy can include H2 C═CHCH2 O, (CH3)2 C═CHCH2 O, (CH3)CH═CHCH2 O, (CH3)CH=C(CH3)CH2 O and CH2 ═CHCH2 CH2 O;
alkynyl can include ethynyl, 1-propynyl, 3-propynyl and the several butynyl, pentynyl and hexynyl isomers, 2,7-octadiynyl and 2,5,8-decatriynyl;
alkynyloxy can include HC.tbd.CCH2 O, CH3 C.tbd.CCH2 O and CH3 C.tbd.CCH2 OCH2 O;
alkylthio can include, methylthio, ethylthio, and the several propylthio, butylthio, pentylthio and hexylthio isomers;
alkylsulfonyl can include CH3 SO2, CH3 CH2 SO2, CH3 CH2 CH2 SO2, (CH3)2 CHSO2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers;
alkylsulfinyl can include CH3 SO, CH3 CH2 SO, CH3 CH2 CH2 SO, (CH3)2 CHSO and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers;
carboxylate can include CH3 CO2 CH3 CH2 CO2, C6 H5 CO2, (C6 H5)CH2 CO2 ;
aryl can include phenyl, p-tolyl and p-fluorophenyl;
alkoxide can include methoxide, t-butoxide, and phenoxide;
diketonates can include acetylacetonate and 2,4-hexanedionate;
sulfonate can include trifluoromethanesulfonate, tosylate, and mesylate;
phosphine can include trimethylphosphine, triphenylphosphine, and methyldiphenylphosphine;
phosphite can include trimethylphosphite, triphenylphosphite, and methyldiphenylphosphite;
phosphinite can include triphenylphosphinite, and methyldiphenylphosphinite;
arsine can include triphenylarsine and trimethylarsine;
stibine can include triphenylstibine and trimethylstibine;
amine can include trimethylamine, triethylamine and dimethylamine;
ether can include (CH3)3 CCH2 OCH2 CH3, THF, (CH3)3 COC(CH3)3, CH3 OCH2 CH2 OCH3, and CH3 OC6 H5 ;
thioether can include CH3 SCH3, C6 H5 SCH3, CH3 OCH2 CH2 SCH3, and tetrahydrothiophene;
amide can include HC(═O)N(CH3)2 and (CH3)C(═O)N(CH3)2 ;
sulfoxide can include CH3 S(═O)CH3, (C6 H5)2 SO;
alkoxy can include methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers, cycloalkoxy can include cyclopentyloxy and cyclohexyloxy;
cycloalkyl can include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; and
cycloalkenyl can include cyclopentenyl and cyclohexenyl.
The term "halogen" or "halide", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine.
Alkoxyalkyl can include CH3 OCH2, CH3 OCH2 CH2, CH3 CH2 OCH2 CH3 CH2 CH2 CH2 OCH2 and CH3 CH2 OCH2 CH2 ; and
alkoxycarbonyl can include CH3 OC(═O), CH3 CH2 OC(═O), CH3 CH2 CH2 OC(═O), (CH3)2 CHOC(═O) and the different butoxy-, pentoxy- or hexyloxycarbonyl isomers.
A neutral electron donor is any ligand which, when removed from a metal center in its closed shell electron configuration, has a neutral charge, i.e., is a Lewis base.
An anionic ligand is any ligand which when removed from a metal center in its closed shell electron configuration has a negative charge. The critical feature of the carbene compounds of this invention is the presence of the ruthenium or osmium in the +2 oxidation state, an electron count of 16 and pentacoordination. A wide variety of ligand moieties X, X1, L, and L1 can be present and the carbene compound will still exhibit its catalytic activity.
A preferred embodiment of the compounds of the present invention is:
A compound of the invention of Formula I wherein:
R and R1 are independently selected from hydrogen, vinyl, C1 -C10 alkyl, aryl, C1 -C10 carboxylate, C2 -C10 alkoxycarbonyl, C1 -C10 alkoxy, aryloxy, each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy;
X and X1 are independently selected from halogen, hydrogen, or C1 -C20 alkyl, aryl, C1 -C20 alkoxide, aryloxide, C2 -C20 alkoxycarbonyl, arylcarboxylate, C1 -C20 carboxylate, aryl or C1 -C20 alkylsulfonate, C1 -C20 alkylthio, C1 -C20 alkylsulfonyl, C1 -C20 alkylsulfinyl, each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy; and
L and L1 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine or thioether.
A more preferred embodiment of Formula I comprises:
A compound of the invention wherein:
R and R1 are independently selected from hydrogen; vinyl, C1 -C5 alkyl, phenyl, C2 -C5 alkoxycarbonyl, C1 -C5 carboxylate, C1 -C5 alkoxy, phenoxy; each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy;
X and X1 are independently selected from Cl, Br, H, or benzoate, C1 -C5 carboxylate, C1 -C5 alkyl, phenoxy, C1 -C5 alkoxy, C1 -C5 alkylthio, aryl, and C1 -C5 alkyl sulfonate; each optionally substituted with C1 -C5 alkyl or a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy;
L and L1 are independently selected from aryl or C1 -C10 alkylphosphine, aryl- or C1 -C10 alkylsulfonated phosphine, aryl- or C1 -C10 alkylphosphinite, aryl- or C1 -C10 alkylphosphonite, aryl- or C1 -C10 alkylphosphite, aryl- or C1 -C10 alkylarsine, aryl- or C1 -C10 alkylamine, pyridine, aryl- or C1 -C10 alkyl sulfoxide, aryl- or C1 -C10 alkylether, or aryl- or C1 -C10 alkylamide, each optionally substituted with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy.
A further preferred embodiment of Formula I comprises:
A compound of the present invention wherein:
R and R1 are independently vinyl, H, Me, Ph;
X and X1 are independently Cl, CF3 CO2, CH3 CO2, CH3 CO2 CFH2 CO2, (CH3)3 CO, (CF3)2 (CH3) CO, (CF3)(CH3)2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate; and
L and L1 are independently PMe3, PPh3, P(p-Tol)3, P(o-Tol)3, PMePh2, PPhMe2, P(CF3)3, P(p-FC6 H4)3, pyridine, P(P-CF3 C6 H4)3, (p-F)pyridine, (p-CF3)pyridine, P (C6 H4 -SO3 Na)3 or P(CH2 C6 H4 -SO3 Na)3.
For any of the foregoing described preferred groups of compounds, any 2, 3, or 4 of X, X1, L, L1 can be taken together to form a chelating multidentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates. Specific examples include Ph2 PCH2 CH2 PPh2, Ph2 AsCH2 CH2 AsPh2, Ph2 PCH2 CH2 C(CF3)O--, binaphtholate dianions, pinacolate dianions, Me2 P(CH2)2 PMe2 and - OC(CH3)2 (CH3)2 CO-. Preferred bidentate ligands are Ph2 PCH2 CH2 PPh2 and Me2 PCH2 CH2 PMe2. Tridentate ligands include, but are not limited to, (CH3)2 NCH2 CH2 P(Ph)CH2 CH2 N(CH3)2. Other preferred tridentate ligands are those in which X, L, and L1 are taken together to be cyclopentadienyl, indenyl or fluorenyl, each optionally substituted with C2 -C20 alkenyl, C2 -C20 alkynyl, C1 -C20 alkyl, aryl, C1 -C20 carboxylate, C1 -C20 alkoxy, C2 -C20 alkenyloxy, C2 -C20 alkynyloxy, aryloxy, C2 -C20 alkoxycarbonyl, C1 -C20 alkylthio, C1 -C20 alkylsulfonyl, C1 -C20 alkylsulfinyl, each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy. More preferably in compounds of this type, X, L, and L1 are taken together to be cyclopentadienyl or indenyl, each optionally substituted with hydrogen; vinyl, C1 -C10 alkyl, aryl, C1 -C10 carboxylate, C2 -C10 alkoxycarbonyl, C1 -C10 alkoxy, aryloxy, each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy. Most preferably, X, L, and L1 are taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, Me or Ph. Tetradentate ligands include, but are not limited to O2 C(CH2)2 P(Ph)(CH2)2 P(Ph)(CH2)2 CO2, phthalocyanines, and porphyrins.
The most preferred carbene compounds of the present invention include: ##STR9##
The compounds of the present invention can be prepared in several different ways, each of which is described below.
The most general method for preparing the compounds of this invention comprises reacting (XX1 MLn L1m)p with a cyclopropene or phosphorane in the presence of a solvent to produce a carbene complex, as shown in the equations. ##STR10## wherein: M, X, X1, L, L1, n, m, p, R2, R3, R4, R5, and R6 are as defined above. Preferably, R2, R3, R4, R5, and R6 are independently selected from the group consisting of C1 -C6 alkyl or phenyl.
Examples of solvents for this reaction include organic, protic, or aqueous solvents which are inert under the reaction conditions, such as: aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Preferred solvents include benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, water, or mixtures thereof. More preferably, the solvent is benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, or mixtures thereof.
A suitable temperature range is from about -20°C to about 125°C, preferably 35°C to 90°C, and more preferably 50°C to 65°C Pressure is not critical but may depend on the boiling point of the solvent used, i.e., use sufficient pressure to maintain a solvent liquid phase. Reaction times are not critical, and can be from several minutes to 48 hours. The reactions are generally carried out in an inert atmosphere, most preferably nitrogen or argon.
The reaction is usually carried out by dissolving the compound (XX1 MLn L1 m)p, in a suitable solvent, adding the cyclopropene (preferably in a solvent) to a stirred solution of the compound, and optionally heating the mixture until the reaction is complete. The progress of the reaction can be monitored by any of several standard analytical techniques, such as infrared or nuclear magnetic resonance. Isolation of the product can be accomplished by standard procedures, such as evaporating the solvent, washing the solids (e.g., with alcohol or benzene), and then recrystallizing the desired carbene complex. Whether the moieties X, X1, L, or L1 are (unidentare) ligands or some taken together to form multidentate ligands will depend on the starting compound which simply carries these ligands over into the desired carbene complex.
In one variation of this general procedure, the reaction is conducted in the presence of HgCl2, preferably 0.01 to 0.2 molar equivalents, more preferably 0.05 to 0.1 equivalents, based on XX1 MLn L1 m. In this variation, the reaction temperature is preferably 15°C to 65°C
In a second variation of the general procedure, the reaction is conducted in the presence of ultraviolet radiation. In this variation, the reaction temperature is preferably -20°C to 30°C
It is also possible to prepare carbene complexes of this invention by ligand exchange. For example, L and/or L1 can be replaced by a neutral electron donor, L2, in compounds of Formula I by reacting L2 with compounds of Formula I wherein L, L1, and L2 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine or thioether. Similarly, X and/or X1 can be replaced by an anionic ligand, Y, in compounds of Formula I by reacting M1 Y with compounds of Formula I, wherein X and X1 are independently selected from halogen, hydrogen, or C1 -C20 alkyl, aryl, C1 -C20 alkoxide, aryloxide, C2 -C20 alkoxycarbonyl, arylcarboxylate, C1 -C20 carboxylate, aryl or C1 -C20 alkylsulfonate, C1 -C20 alkylthio, C1 -C20 alkylsulfonyl, C1 -C20 alkylsulfinyl, each optionally substituted with C1 -C5 alkyl, halogen, C1 -C5 alkoxy or with a phenyl group optionally substituted with halogen, C1 -C5 alkyl or C1 -C5 alkoxy. These ligand exchange reactions are typically carried out in a solvent which is inert under the reaction conditions. Examples of solvents include those described above for the preparation of the carbene complex.
The compounds of this invention are useful as catalysts in the preparation of a wide variety of polymers which can be formed by ring-opening metathesis polymerization of cyclic olefins. Therefore, one embodiment of this invention is an improved polymerization process comprising metathesis polymerization of a cyclic olefin, wherein the improvement comprises conducting the polymerization in the presence of a catalytic amount of a compound of Formula I. The polymerization reaction is exemplified for norbornene in the following equation: ##STR11## wherein n is the repeat unit of the polymeric chain.
Examples of cyclic olefins for this polymerization process include norbornene, norbornadiene, cyclopentene, dicyclopentadiene, cycloheptene, cyclo-octene, 7-oxanorbornene, 7-oxanorbornadiene, and cyclododecene.
The polymerization reaction is generally carried out in an inert atmosphere by dissolving a catalytic amount of a compound of Formula I in a solvent and adding the cyclic olefin, optionally dissolved in a solvent, to the catalyst solution. Preferably, the reaction is agitated (e.g., stirred). The progress of the reaction can be monitored by standard techniques, e.g., nuclear magnetic resonance spectroscopy.
Examples of solvents for the polymerization reaction include organic, protic, or aqueous solvents which are inert under the polymerization conditions, such as: aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Preferred solvents include benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, water, or mixtures thereof. More preferably, the solvent is benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, or mixtures thereof. Most preferably, the solvent is toluene or a mixture of benzene and methylene chloride. The solubility of the polymer formed in the polymerization reaction will depend on the choice of solvent and the molecular weight of the polymer obtained.
Reaction temperatures can range from 0°C to 100°C, and are preferably 25°C to 45°C The ratio of catalyst to olefin is not critical, and can range from 1:5 to 1:10,000, preferably 1:10 to 1:1,000.
Because the compounds of Formula I are stable in the presence of protic solvents, the polymerization reaction may also be conducted in the presence of a protic solvent. This is very unusual among metathesis catalysts and provides a distinct advantage for the process of this invention over the processes of the prior art. Other advantages of the polymerization process of this invention derive from the fact that the compounds of Formula I are well-defined, stable Ru or Os carbene complexes providing high catalytic activity. Using such compounds as catalysts allows control of the rate of initiation, extent of initiation, and the amount of catalyst. Also, the well-defined ligand environment of these complexes provides flexibility in modifying and fine-tuning their activity level, solubility, and stability. In addition, these modifications enable ease of recovery of catalyst.
A 50 ml Schlenk flask equipped with a magnetic stirbar is charged with (MXX1 Ln L1 m)p (0.1 mmol) inside a nitrogen-filled drybox. Methylene chloride (2 ml) is added to dissolve the complex followed by 25 ml of benzene to dilute the solution. One equivalent of a cyclopropene is then added to this solution. The reaction flask is then capped with a stopper, removed from the box, attached to a reflux condenser under argon and heated at 55°C The reaction is then monitored by NMR spectroscopy until all the reactants have been converted to product. At the end of the reaction, the solution is allowed to cool to room temperature under argon and then filtered into another Schlenk flask via a cannula filter. All solvent is then removed in vacuo to give a solid. This solid is then washed with a solvent in which the by-product will be soluble but the desired product will not. After the washing supernatant is removed, the resulting solid powder is dried in vacuo overnight. Further purification via crystallization can be performed if necessary.
The abbreviations Me, Ph, and THF used herein refer to methyl, phenyl, and tetrahydrofuran, respectively.
Representative compounds of the present invention which are prepared in accordance with the procedure described above are exemplified in Table I.
| TABLE I |
| __________________________________________________________________________ |
| ##STR12## |
| Compound Name M X X1 |
| L L1 |
| R R1 |
| __________________________________________________________________________ |
| Dichloro-3,3-diphenylvinyl- |
| Ru Cl Cl PPh3 |
| PPh3 |
| H CHCPH2 |
| carbene-bis(triphenylphos- |
| phine)ruthenium(II) |
| Dibromo-3,3-diphenylvinyl- |
| Ru Br Br PPh3 |
| PPh3 |
| H CHCPh2 |
| carbene-bis(triphenylphos- |
| phine)ruthenium(II) |
| Dichloro-3,3-diphenylvinyl- |
| Ru Cl Cl PPh2 Me |
| PPh2 Me |
| H CHCPh2 |
| carbene-bis(methyldiphenyl- |
| phosphine)ruthenium(II) |
| Dibromo-3,3-diphenylvinyl- |
| Ru Br Br PPh2 Me |
| PPh2 Me |
| H CHCPH2 |
| carbene-bis(methyldiphenyl- |
| phosphine)ruthenium(II) |
| Dichloro-3-methyl-3- phenylvinylcarbene- bis(triphenylphosphine)- |
| ruthenium(II) Ru Cl Cl PPh3 |
| PPh3 |
| H |
| ##STR13## |
| Dibromo-3-methyl-3- phenylvinylcarbene- bis(triphenylphosphine)- ruthenium |
| (II) Ru Br Br PPh3 |
| PPh3 |
| H |
| ##STR14## |
| Dichloro-3,3-dimethyl- vinylcarbene-bis(triphenyl- phosphine)ruthenium(II) |
| . Ru Cl Cl PPh3 |
| PPh3 |
| H |
| ##STR15## |
| Bis(acetato)-3,3-diphenyl- vinylcarbene-bis(triphenyl- phosphine)ruthenium |
| (II) Ru |
| ##STR16## |
| ##STR17## |
| PPh3 |
| PPh3 |
| H |
| ##STR18## |
| Acetato-3,3-diphenyl- phosphine)ruthenium(II)- chloride |
| Ru |
| ##STR19## |
| Cl PPh3 |
| PPh3 |
| H |
| ##STR20## |
| 3,3-Diphenylvinylcarbene- bis(trifluoroacetato)bis- (triphenylphosphine)- |
| uthenium(II) Ru |
| ##STR21## |
| ##STR22## |
| PPh3 |
| PPh3 |
| H |
| ##STR23## |
| 3,3-Diphenylvinylcarbene- n2 -pinacol-bis(triphenyl- phosphine)ruthen |
| ium(II) Ru |
| ##STR24## PPh3 |
| PPh3 |
| H |
| ##STR25## |
| 3,3-Diphenylvinylcarbene- bis(t-butoxy)bis-(tri- phenylphosphine |
| ruthenium- (II) |
| Ru Me3 CO |
| Me3 CO |
| PPh3 |
| PPh3 |
| H |
| ##STR26## |
| 3,3-Diphenylvinylcarbene- bis(2-trifluoromethyl-2- propoxy)-bis(triphenyl- |
| phosphine)ruthenium(II) |
| Ru |
| ##STR27## |
| ##STR28## |
| PPh3 |
| PPh3 |
| H |
| ##STR29## |
| __________________________________________________________________________ |
| These are representative examples of the ruthenium complexes. Analogous |
| complexes could be made with osmium. |
In a typical reaction, a 200 ml Schlenk flask equipped with a magnetic stirbar was charged with RuCl2 (PPh3)4 (6.00 g, 4.91 mmol) inside a nitrogen-filled drybox. Methylene chloride (40 mL) was added to dissolve the complex followed by 100 mL of benzene to dilute the solution. 3,3-Diphenylcyclopropene (954 mg, 1.01 equiv) was then added to the solution via pipette. The reaction flask was capped with a stopper, removed from the box, attached to a reflux condenser under argon and heated at 53°C for 11 h. After allowing the solution to cool to room temperature, all the solvent was removed in vacuo to give a dark yellow-brown solid. Benzene (10 mL) was added to the solid and subsequent swirling of the mixture broke the solid into a fine powder. Pentane (80 mL) was then slowly added to the mixture via cannula while stirring vigorously. The mixture was stirred at room temperature for 1 h and allowed to settle before the supernatant was removed via cannula filtration. This washing procedure was repeated two more times to ensure the complete removal of all phosphine by-products. The resulting solid was then dried under vacuum overnight to afford 4.28 g (98%) of Compound 1 as a yellow powder with a slight green tint. 1 H NMR (C6 D6): δ17.94 (pseudo-quartet=two overlapping triplets, 1H, Ru═CH, JHH =10.2 Hz, JPH =9.7 Hz), 8.33(d, 1H, CH=CPh2, JHH 10.2 Hz). 31 P NMR (C6 D6): δ28.2 (s). 13 C NMR(CD2 Cl2): δ288.9 (t, M=C, JCP =10.4 Hz), 149.9 (t, CH═CPh2, JCP =11.58 Hz).
The carbene complex which is the compound formed in the above example is stable in the presence of water or alcohol.
PAC Synthesis procedure for ##STR31##A 50 ml Schlenk flask equipped with a magnetic stirbar was charged with OsCl2 (PPh3)3 (100 mg, 0.095 mmol) inside a nitrogen-filled drybox. Methylene chloride (2 ml) was added to dissolve the complex followed by 25 ml of benzene to dilute the solution. 3,3-diphenylcyclopropene (18.53 mg, 1.01 eq) was then added to the solution via piper. The reaction flask was capped with a stopper, removed from the box, attached to a reflux condenser under argon and heated at 55°C for 14 h. After allowing the solution to cool to room temperature, all the solvent was removed in vacuo to give a dark yellow-brown solid. Benzene (2 ml) was added to the solid and subsequent swirling of the mixture broke the solid into a fine powder. Pentane (30 ml) was then slowly added to the mixture via cannula while stirring vigorously. The mixture was stirred at RT for 1 h and allowed to settle before the supernatant was removed via cannula filtration. This washing procedure was repeated two more times to ensure the complete removal of all phosphine by-products. The resulting solid was then dried under vacuum overnight to afford 74.7 mg of Compound 2 as a yellow powder (80%). 1 H NMR (C6 D6): δ19.89 (pseudo-quartet=two overlapping triplets, 1H, Os═CH, JHH =10.2 Hz), 8.23 (d, 1H, CH═CPh2, JHH =10.2 Hz). 31 P NMR (C6 D6): δ4.98 (s) .
PAC Synthesis of ##STR32##A 50 ml Schlenk flask equipped with a magnetic stirbar was charged with RuCl2 (PPh3)2 (═CH-CH═CPPh2) (100 mg, 0.18 mmol) inside a nitrogen-filled drybox. Methylene chloride (10 ml) was added to dissolve the complex. AgCF3 CO2 (24.9 mg., 1 eq) was weighed into a 10 ml round-bottom flask, dissolved with 3 ml of THF. Both flasks were then capped with rubber septa and removed from the box. The Schlenk flask was then put under an argon atmosphere and the AgCF3 CO2 solution was added dropwise to this solution via a gas-tight syringe over a period of 5 min while stirring. At the end of the addition, there was a lot of precipitate in the reaction mixture and the solution turned into a fluorescent green color. The supernatant was transferred into another 50 ml Schlenk flask under argon atmosphere via the use of a cannula filter. Subsequent solvent removal under in vacuo and washing with pentane (10 ml) afforded a green solid powder, Compound 3. IV 92.4 mg (85%) . 1 H NMR (2:2:1 CD2 Cl2 :C6 D6 :THF-d8) :δ18.77 (dt, 1H, Ru═CH, JHH =11.2 Hz, JPH =8.6 Hz), 8.40 (d, 1H), CH═CPh2, JHH =11.2 Hz). 31 P NMR (2:2:1 CD2 Cl2 : C6 D6 :THF-d8)δ29.4. 19 F NMR (2:2:1 CD2 Cl2 :C6 D6 :THF-d8) δ75.8.
PAC Synthesis of ##STR33##A 50 ml Schlenk flask equipped with a magnetic stirbar was charged with RuCl2 (PPh3)2 (═CH--CH═CPh2) (100 mg, 0.11 mmol) inside a nitrogen-filled drybox. Methylene chloride (10 ml) was added to dissolve the complex. AgCF3 CO2 (49.8 mg, 2 eq) was weighed into a 10 ml round-bottom flask, dissolved with 4 ml of THF. Both flasks were then capped with rubber septa and removed from the box. The Schlenk flask was then put under an argon atmosphere and the AgCF3 CO2 solution was added dropwise via a gas tight syringe over a period of 5 min to the solution of ruthenium compound while stirring. At the end of the addition, there was a lot of precipitate in the reaction mixture and the solution turned into a fluorescent lime green color. The supernatant was transferred into another 50 ml Schlenk flask under argon atmosphere with the use of a cannula filter. Subsequent solvent removal in vacuo and washing with pentane (10 ml) afforded a green powder, Compound 4. Yield =102 mg (87%). 1 H NMR (2:2:1 CD2 Cl2 :C6 D6 :THF-d8) δ19.23 (dt, slightly overlapping) Ru═CH, JHH =11.5 Hz, JPH =5.4 Hz), 8.07 (d, 1H, CH═CPH2, JHH 11.5 Hz). 31 P NMR (2:2:1 CD2 Cl2 :C6 D6 :THF-d8) δ28.6. 19 F NMR (2:2:1 CD2 Cl2 :C6 D6:THF-d8) δ-75.7.
PAC Synthesis of ##STR34##The reaction between [Ru(C5 Me5)Cl]4 and 3,3-diphenylcyclopropene was done under a nitrogen atmosphere. [Ru(C5 Me5)Cl]4 (100 mg, 0.092 mmoL) was dissolved in 10 mL of tetrahydrofuran. To this solution was added 3,3-diphenylcyclopropene (350 rag, 1.82 mmoL). The resulting solution was stirred at room temperature for 1 h. Petroleum ether (10 mL) was then added to the reaction mixture. It was stirred for an additional 30 min, and then all volatile components were removed from the reaction mixture under vacuum. The crude product was extracted with diethyl ether; volatiles were removed from the filtrate under vacuum to afford a dark colored, oily solid. This was further extracted with petroleum ether; volatiles were removed from the filtrate under vacuum to afford a very dark red-brown oil. This was recrystallized from petroleum ether at -40°C to afford dark crystals. NMR spectra of which are consistent with the formulation [Ru(C5 Me5)(CHC═CPh2)Cl]n (value of n as yet undetermined: e.g., the product could be a dimer).
PAC Polymerization of Norbornene Using Compound of Example 1(PPh3)2 Cl2 Ru═CH--CH═CPh2 catalyzed polymerized norbornene in a 1.8 mixture of CH2 Cl2 /C6 H6 at room temperature to yield polynorbornene. A new signal, attributed to Hα of the propagating carbene, was observed by 1 H NMR spectroscopy at 17.79 ppm. Its identity and stability was confirmed by preparing a block polymer with 2,3-dideuteronorbornene and perprotionorbornene. When 2,3-dideuteronorbornene was added to the propagating species,, the new carbene signal vanished and then reappeared when perprotionorbornene was added for the third block.
PAC Polymerization of Norbornene Using Compound of Example 5Ru(C5 Me5)(CHC═CPh2)Cl (14 mg, 0.030 mmoL) was dissolved in 1 mL of perdeuterated toluene under a nitrogen atmosphere. To this was added norbornene (109 mg, 1.16 mmoL). The reaction mixture became viscous within minutes as the norbornene polymerized. After 20 hrs at room temperature a 1 H NMR spectrum of the reaction mixture was recorded, which showed polynorbornene and unreacted norbornene monomer in a ratio of 82:12.
Grubbs, Robert H., Nguyen, Sonbinh T., Johnson, Lynda K.
| Patent | Priority | Assignee | Title |
| 10000442, | Mar 27 2014 | Trent University | Certain metathesized natural oil triacylglycerol polyols for use in polyurethane applications and their related properties |
| 10000601, | Mar 27 2014 | Trent University | Metathesized triacylglycerol polyols for use in polyurethane applications and their related properties |
| 10000724, | Mar 27 2014 | Trent University | Metathesized triacylglycerol green polyols from palm oil for use in polyurethane applications and their related properties |
| 10059857, | Jun 12 2012 | Materia, Inc. | Method and composition for improving adhesion of metathesis compositions to substrates |
| 10239965, | Feb 12 2015 | Materia, Inc. | Cyclic olefin resin compositions comprising functional elastomers |
| 10259210, | Oct 21 2014 | Statasys Ltd. | Three-dimensional inkjet printing using ring-opening metathesis polymerization |
| 10344118, | Feb 14 2015 | Materia, Inc. | Romp polymers having improved resistance to hydrocarbon fluids |
| 10457597, | Jun 17 2011 | MATERIA, INC | Adhesion promoters and gel-modifiers for olefin metathesis compositions |
| 10538804, | Jun 15 2009 | ANDE CORPORATION | Methods for forensic DNA quantitation |
| 10589511, | Oct 21 2014 | STRATASYS LTD. | Three-dimensional inkjet printing using ring-opening metathesis polymerization |
| 10619003, | Sep 04 2013 | California Institute of Technology | Functionalized linear and cyclic polyolefins |
| 10633484, | Jan 10 2014 | MATERIA, INC | Method and composition for improving adhesion of metathesis compositions to substrates |
| 10689582, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining natural oil feedstocks |
| 10711090, | Jun 24 2013 | MATERIA, INC | Thermal insulation |
| 10745347, | Apr 24 2012 | Stepan Company | Unsaturated fatty alcohol derivatives from natural oil metathesis |
| 10774035, | Sep 23 2016 | Umicore AG & Co KG | Preparation of amino acids and amino acid derivatives |
| 10799613, | Oct 30 2013 | California Institute of Technology | Direct photopatterning of robust and diverse materials |
| 10907018, | Feb 27 2014 | MATERIA, INC | Adhesion promoter compositions for cyclic olefin resin compositions |
| 11001725, | Feb 05 2016 | STRATASYS LTD.; STRATASYS LTD | Three-dimensional inkjet printing using ring-opening metathesis polymerization |
| 11022555, | May 12 2011 | ANDE CORPORATION | Methods and compositions for rapid multiplex application of STR loci |
| 11097529, | Oct 21 2014 | STRATASYS LTD. | Three-dimensional inkjet printing using ring-opening metathesis polymerization |
| 11110461, | Apr 04 2007 | ANDE CORPORATION | Integrated nucleic acid analysis |
| 11118004, | Apr 26 2016 | STRATASYS LTD. | Three-dimensional inkjet printing using ring-opening metathesis polymerization |
| 11124524, | Sep 30 2011 | SOLUTIA CANADA INC | Diarylethene compounds and uses thereof |
| 11173653, | Feb 05 2016 | STRATASYS LTD. | Three-dimensional inkjet printing using polyamide-forming materials |
| 11179879, | Feb 07 2016 | STRATASYS LTD | Three-dimensional printing combining ring-opening metathesis polymerization and free radical polymerization |
| 11441173, | Jun 15 2009 | ANDE CORPORATION | Optical instruments and systems for forensic DNA quantitation |
| 11549084, | Oct 31 2017 | LG Chem, Ltd | Cleaning liquid composition and method for cleaning polymerization apparatus using same |
| 11655386, | Feb 05 2016 | STRATASYS LTD. | Three-dimensional inkjet printing using ring-opening metathesis polymerization |
| 11760889, | Apr 24 2012 | Stepan Company | Unsaturated fatty alcohol derivatives from natural oil metathesis |
| 5710298, | Apr 03 1992 | MATERIA, INC | Method of preparing ruthenium and osmium carbene complexes |
| 5728785, | Jul 02 1996 | California Institute of Technology | Romp polymerization in the presence of peroxide crosslinking agents to form high-density crosslinked polymers |
| 5728917, | Apr 03 1992 | MATERIA, INC | Polymer depolymerization using ruthenium and osmium carbene complexes |
| 5750815, | Apr 03 1992 | MATERIA, INC | Olefin metathesis coupling using ruthenium and osmium carbene complexes |
| 5811515, | May 29 1996 | California Institute of Technology | Synthesis of conformationally restricted amino acids, peptides, and peptidomimetics by catalytic ring closing metathesis |
| 5831108, | Jul 31 1996 | California Institute of Technology | High metathesis activity ruthenium and osmium metal carbene complexes |
| 5840238, | May 14 1996 | Ciba Specialty Chemicals Corporation | Process for the manufacture of fibre-reinforced composites |
| 5840820, | Apr 13 1995 | NORTH CAROLINA AT CHAPEL HILL, UNIVERSITY OF | Olefin metathesis reactions in carbon dioxide medium |
| 5849851, | Apr 03 1992 | MATERIA, INC | Romp of functionalized cyclic olefins using ruthenium and osmium carbene complexes |
| 5880231, | Apr 03 1992 | MATERIA, INC | Synthesis of telechelic polymers using ruthenium and osmium carbene complexes |
| 5916983, | May 27 1997 | Bend Research, Inc. | Biologically active compounds by catalytic olefin metathesis |
| 5917071, | Nov 15 1996 | California Institute of Technology | Synthesis of ruthenium or osmium metathesis catalysts |
| 5922863, | Apr 03 1992 | MATERIA, INC | Diene cyclization using ruthenium and osmium carbene complexes |
| 5932664, | Dec 23 1996 | Bayer AG | Process for the production of hydrogenated ring-opened metathesis polymers |
| 5939504, | Dec 07 1995 | CYMETECH, LLC, A DELAWARE LIMITED LIABILITY COMPANY | Method for extending the pot life of an olefin metathesis polymerization reaction |
| 5969170, | Apr 03 1992 | MATERIA, INC | High activity ruthenium and osmium metal carbene complexes for olefin metathesis reactions |
| 6020443, | Feb 08 1996 | Cymetech, LLC | Polymerization of low grade DCPD monomers using an olefin metathesis catalyst |
| 6040363, | Sep 05 1997 | ABELL, III , NELSON D | Metathesis polymerizered olefin composites including sized reinforcement material |
| 6048993, | Nov 15 1996 | California Institute of Technology | Synthesis of ruthenium or osmium metathesis catalysts |
| 6071459, | Sep 05 1997 | A O SMITH CORPORATION | Process of making metathesis polymerized olefin articles containing flame-retarding agents |
| 6077805, | Mar 06 1997 | Ciba Specialty Chemicals Corporation | Hexacoordinated ruthenium or osmium carbene catalysts |
| 6080826, | Jan 06 1997 | California Institute of Technology | Template-directed ring-closing metathesis and ring-opening metathesis polymerization of functionalized dienes |
| 6107420, | Jul 31 1998 | California Institute of Technology | Thermally initiated polymerization of olefins using Ruthenium or osmium vinylidene complexes |
| 6111121, | Aug 03 1995 | California Institute of Technolgy | High metathesis activity ruthenium and osmium metal carbene complexes |
| 6147026, | Nov 15 1996 | Ciba Specialty Chemcials Corporation | Catalyst mixture for the ring-opening metathesis polymerisation |
| 6156692, | Apr 30 1996 | BP Amoco Corporation | Ruthenium-containing catalyst composition for olefin metathesis |
| 6159890, | Apr 30 1996 | BP Amoco Corporation | Ruthenium-containing catalyst system for olefin metathesis |
| 6171995, | Nov 15 1996 | Ciba Specialty Chemcials Corporation | Catalyst mixture for ring-opening metathesis polymerization |
| 6175047, | Dec 26 1997 | Takasago International Corporation | Ruthenium metathesis catalyst and method for producing olefin reaction product by metathesis reaction using the same |
| 6177464, | Mar 14 1997 | SEPRACOR, INC | Ring opening metathesis of alkenes |
| 6211391, | Aug 03 1995 | ABELL, NELSON D , III | High metathesis activity ruthenium and osmium metal carbene complexes |
| 6215019, | Sep 01 1998 | MATERIA, INC | Synthesis of 5-decenyl acetate and other pheromone components |
| 6232482, | Aug 22 1997 | BASF Aktiengesellschaft | Method for producing ruthenium complexes |
| 6271315, | Jun 17 1999 | Wisconsin Alumni Research Foundation | Methods for making multivalent arrays |
| 6291616, | Jun 17 1999 | Wisconsin Alumni Research Foundation | Methods and reagents for capping ruthenium or osmium carbene-catalyzed ROMP products |
| 6313365, | May 15 1998 | Takasago International Corporation | Ruthenium metathesis catalyst and method for producing olefin reaction product by metathesis reaction using the same |
| 6323296, | Sep 05 1997 | Metathesis polymerized olefin composites including sized reinforcement material | |
| 6359129, | Aug 15 2000 | University of Kansas | Amino acid-derived, 7-membered cyclic sulfamides and methods of synthesizing the same |
| 6376690, | Sep 09 1998 | California Institute of Technology | Method of removing transition metals |
| 6383319, | Aug 07 1998 | A P T AEROSPACE, LLC; A P T AEROSPACE, L L C , A LOUISIANA CORP | Rocket fuels based on metal hydrides and poly-DCPD |
| 6391978, | Dec 14 2000 | Bayer Corporation | Process for the synthesis of hydroxyl-end group functionalized polybutadienes |
| 6409875, | Feb 05 1999 | MATERIA, INC | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| 6410110, | Sep 05 1997 | Cymetech, LLC | Pipe made from metathesis polymerized olefins |
| 6410666, | Mar 18 1999 | California Institute of Technology | ABA triblock and diblock copolymers and methods of preparing the same |
| 6414097, | Jan 26 1999 | California Institute of Technology | Methods for cross-methathesis of terminal olefins |
| 6420586, | Aug 15 2000 | University of Kansas | Amino acid-derived cyclic phosphonamides and methods of synthesizing the same |
| 6420592, | Aug 15 2000 | University of Kansas | Amino acid-derived phosponamidic anhydrides and methods of preparing the same |
| 6426419, | Mar 31 1999 | California Institute of Technology | Ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity |
| 6465554, | Mar 31 1998 | Ciba Specialty Chemicals Corporation | Ruthenium and osmium carbene carbonyl catalysts |
| 6476167, | Dec 14 2000 | Bayer Corporation | END-FUNCTIONALIZED POLYOLEFIN PREPARED VIA RING OPENING METATHESIS POLYMERIZATION IN THE PRESENCE OF A NOVEL CHAIN TRANSFER AGENT, AND A PROCESS FOR THE PREPARATION OF THE END-FUNCTIONALIZED POLYOLEFIN VIA RING OPENING METATHESIS POLYERMIZATION |
| 6486324, | Mar 14 1997 | Sepracor Inc. | Ring opening metathesis of alkenes |
| 6504041, | Nov 15 1996 | California Institute of Technology | Synthesis of ruthenium or osmium metathesis catalysts |
| 6515084, | Aug 03 1995 | California Institute of Technology | High metathesis activity ruthenium and osmium metal carbene complexes |
| 6518330, | Feb 13 2001 | Board of Trustees of University of Illinois | Multifunctional autonomically healing composite material |
| 6525125, | Feb 05 1999 | MATERIA, INC | Polyolefin compositions having variable density and methods for their production and use |
| 6538072, | Jun 17 1999 | Wisconsin Alumni Research Foundation | Methods for making multivalent arrays |
| 6583236, | Feb 05 1999 | Cymetech, LLC | Polyolefin compositions having enhanced ultraviolet and oxidative resistance and methods for their production and use |
| 6610626, | Sep 05 2000 | MATERIA, INC | Highly active metathesis catalysts generated in situ from inexpensive and air stable precursors |
| 6624265, | Mar 31 1999 | California Institute of Technology | Ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity |
| 6696536, | Mar 18 1999 | California Institute of Technology | ABA triblock and diblock copolymers and methods of preparing the same |
| 6696597, | Sep 01 1998 | MATERIA, INC | Metathesis syntheses of pheromones or their components |
| 6737531, | Dec 17 2002 | Brookhaven Science Associates, LLC | Catalysts for hydrogenation and hydrosilylation, methods of making and using the same |
| 6750272, | Jun 25 2001 | Board of Trustees of University of Illinois | Catalyzed reinforced polymer composites |
| 6759537, | Mar 23 2001 | MATERIA, INC | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts |
| 6794534, | Jun 23 2000 | California Institute of Technology | Synthesis of functionalized and unfunctionalized olefins via cross and ring-closing metathesis |
| 6818586, | Aug 01 2001 | MATERIA, INC | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts |
| 6838489, | Mar 23 2001 | Cymetech, LLC | High activity metal carbene metathesis catalysts generated using a thermally activated N-heterocyclic carbene precursor |
| 6858659, | Feb 13 2001 | The Board of Trustess of the University of Illinois | Multifunctional autonomically healing composite material |
| 6872792, | Jun 25 2001 | Lord Corporation | Metathesis polymerization adhesives and coatings |
| 6884859, | Aug 29 2001 | California Institute of Technology | Ring-opening metathesis polymerization of bridged bicyclic and polycyclic olefins containing two or more heteroatoms |
| 6890650, | Jul 23 2002 | PPG Industries Ohio, Inc | Glass fiber sizing compositions, sized glass fibers, and polyolefin composites |
| 6900347, | Sep 01 1998 | MATERIA, INC | Impurity inhibition in olefin metathesis reactions |
| 6939451, | Sep 19 2000 | Monogram Biosciences, Inc | Microfluidic chip having integrated electrodes |
| 6946533, | Aug 01 2002 | California Institute of Technology | Synthesis of macrocyclic polymers by ring insertion polymerization of cyclic olefin monomers |
| 6960272, | Dec 11 1998 | Lord Corporation | Contact metathesis polymerization |
| 6962729, | Dec 11 1998 | Lord Corporation | Contact metathesis polymerization |
| 6973949, | Dec 11 1998 | Lord Corporation | Tire laminate bonded by contact metathesis |
| 7002049, | Aug 19 2002 | Eastman Chemical Company | Process for α,β-dihydroxyalkenes and derivatives |
| 7025851, | Dec 11 1998 | Lord Corporation | Contact metathesis polymerization |
| 7041763, | Jul 14 2000 | SWITCH MATERIALS INC | Photochromic polymers and methods of synthesizing same |
| 7094898, | May 29 2003 | University of Ottawa | Ruthenium compounds, their production and use |
| 7102047, | Aug 03 1995 | California Institute of Technology | High metathesis activity ruthenium and osmium metal carbene complexes |
| 7115688, | Nov 30 1998 | Nanosphere, Inc. | Nanoparticles with polymer shells |
| 7132503, | Jul 28 2003 | Bridgestone Corporation | Removing gelled unsaturated elastomers from polymerization equipment associated with their production |
| 7199252, | Aug 19 2002 | Eastman Chemical Company | Process for α,β-dihydroxyalkenes and derivatives |
| 7205424, | Jun 19 2003 | UNIVERSITY OF NEW ORLEANS RESEARCH AND TECHNOLOGY FOUNDATION, INC | Preparation of ruthenium-based olefin metathesis catalysts |
| 7285593, | May 19 1998 | ABELL, NELSON D , III | Polyolefin compositions optionally having variable toughness and/or hardness |
| 7326380, | Jul 18 2003 | Northwestern University | Surface and site-specific polymerization by direct-write lithography |
| 7329758, | May 24 1999 | California Institute of Technology | Imidazolidine-based metal carbene metathesis catalysts |
| 7339006, | Feb 05 1999 | Cymetech, L.L.C. | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| 7507854, | Sep 01 1998 | MATERIA, INC | Impurity reduction in Olefin metathesis reactions |
| 7534917, | Apr 27 2006 | UNITED STATES OF AMERICA, THE, AS REPRESENTED BY THE SECRETARY OF AGRICULTURE | Method of producing dicarboxylic acids |
| 7566747, | May 07 2004 | Board of Trustees of the University of Illinois, The | Wax particles for protection of activators, and multifunctional autonomically healing composite materials |
| 7569625, | Jun 02 2006 | The Board of Trustees of the University of Illinois | Self-healing elastomer system |
| 7598330, | Apr 05 2002 | California Institute of Technology | Cross-metathesis of olefins directly substituted with an electron-withdrawing group using transition metal carbene catalysts |
| 7612152, | May 06 2005 | The Board of Trustees of the University of Illinois | Self-healing polymers |
| 7622590, | Sep 10 1998 | MATERIA, INC | Catalyst complex with carbene ligand |
| 7683180, | Apr 16 2001 | California Institute of Technology | Group 8 transition metal carbene complexes as enantionselective olefin metathesis catalysts |
| 7723405, | Jan 05 2006 | The Board of Trustees of the University of Illinois | Self-healing coating system |
| 7750172, | Aug 03 1995 | California Institute of Technology | High metathesis activity ruthenium and osmium carbene complexes |
| 7777055, | Aug 09 2002 | SOLUTIA CANADA INC | Photochromic and electrochromic compounds and methods of synthesizing and using same |
| 7902389, | Sep 10 1998 | MATERIA, INC | Catalyst complex with carbene ligand |
| 7956132, | Aug 25 2006 | Dow Global Technologies LLC | Production of telechelic compounds by metathesis depolymerization |
| 7964320, | Feb 05 1999 | Materia, Inc. | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| 8012400, | Jul 18 2003 | Northwestern University | Surface and site-specific polymerization by direct-write lithography |
| 8018593, | Apr 04 2007 | ANDE CORPORATION | Integrated nucleic acid analysis |
| 8048961, | Aug 25 2006 | Dow Global Technologies LLC | Production of metathesis products by amorphous polymer segment interchange |
| 8058351, | May 20 2005 | Bridgestone Corporation | Method for preparing low molecular weight polymers |
| 8153810, | Mar 18 1999 | Evonik Degussa GmbH | Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis |
| 8183415, | Jun 21 2007 | Amgen, Inc. | Methods of synthesizing cinacalcet and salts thereof |
| 8227371, | Sep 24 2010 | ExxonMobil Chemical Patents Inc.; ExxonMobil Chemical Patents INC | Class of olefin metathesis catalysts, methods of preparation, and processes for the use thereof |
| 8241575, | Jan 28 2008 | Johns Hopkins University | Molecularly imprinted polymer sensor device |
| 8324334, | Aug 21 2008 | MATERIA, INC | Telechelic olefin metathesis polymers from renewable feedstocks |
| 8378034, | Aug 04 2008 | Firestone Polymers, LLC | Adducts of metathesis polymers and preparation thereof |
| 8403044, | May 05 2009 | Stepan Company | Sulfonated internal olefin surfactant for enhanced oil recovery |
| 8425861, | Apr 04 2007 | ANDE CORPORATION | Methods for rapid multiplexed amplification of target nucleic acids |
| 8524930, | May 31 2011 | ExxonMobil Chemical Patents Inc.; ExxonMobil Chemical Patents INC | Class of olefin metathesis catalysts, methods of preparation, and processes for the use thereof |
| 8530579, | Aug 25 2006 | Dow Global Technologies Inc; Dow Global Technologies LLC | Production of metathesis products by high melting polymer segment interchange |
| 8536205, | May 25 2005 | SOLUTIA CANADA INC | Photochromic and electrochromic compounds and synthesis and use thereof |
| 8557921, | Aug 25 2006 | Dow Global Technologies Inc; Dow Global Technologies LLC | Production of meta-block copolymers by polymer segment interchange |
| 8597794, | Feb 05 1999 | Materia, Inc. | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| 8604141, | Aug 03 1995 | California Institute of Technology | High metathesis activity ruthenium and osmium metal carbene complexes |
| 8735640, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining and producing fuel and specialty chemicals from natural oil feedstocks |
| 8765893, | Dec 11 2009 | Promerus LLC | Norbornene-type polymers having quaternary ammonium functionality |
| 8765894, | Dec 11 2009 | Promerus LLC | Norbornene-type polymers having quaternary ammonium functionality |
| 8846939, | May 24 1999 | California Institute of Technology | Imidazolidine-based metal carbene metathesis catalysts |
| 8859779, | Sep 10 1998 | MATERIA, INC | Catalyst complex with carbene ligand |
| 8889600, | May 22 2010 | Stepan Company | Sulfonated internal olefin surfactant for enhanced oil recovery |
| 8889932, | Nov 26 2008 | Wilmar Trading Pte Ltd | Methods of producing jet fuel from natural oil feedstocks through oxygen-cleaved reactions |
| 8900671, | Feb 28 2011 | LM WIND POWER US TECHNOLOGY APS | Method for manufacture of an infused spar cap using a low viscosity matrix material |
| 8906999, | Feb 17 2011 | POLYNT COMPOSITES USA INC | Styrene-free unsaturated polyester |
| 8933285, | Nov 26 2008 | Wilmar Trading Pte Ltd | Methods of producing jet fuel from natural oil feedstocks through metathesis reactions |
| 8957268, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining natural oil feedstocks |
| 9000246, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining and producing dibasic esters and acids from natural oil feedstocks |
| 9051519, | Oct 12 2009 | Wilmar Trading Pte Ltd | Diene-selective hydrogenation of metathesis derived olefins and unsaturated esters |
| 9133416, | Dec 22 2011 | Wilmar Trading Pte Ltd | Methods for suppressing isomerization of olefin metathesis products |
| 9139493, | Dec 22 2011 | Wilmar Trading Pte Ltd | Methods for suppressing isomerization of olefin metathesis products |
| 9147844, | Aug 01 2012 | California Institute of Technology | Solvent-free enyne metathesis polymerization |
| 9169174, | Dec 22 2011 | Wilmar Trading Pte Ltd | Methods for suppressing isomerization of olefin metathesis products |
| 9169447, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining natural oils, and methods of producing fuel compositions |
| 9175231, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining natural oils and methods of producing fuel compositions |
| 9181360, | Aug 12 2011 | ExxonMobil Chemical Patents INC | Polymers prepared by ring opening / cross metathesis |
| 9207532, | Oct 05 2012 | California Institute of Technology | Photoinitiated olefin methathesis polymerization |
| 9222056, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining natural oils, and methods of producing fuel compositions |
| 9233365, | Sep 10 1998 | Materia, Inc. | Catalyst complex with carbene ligand |
| 9234985, | Aug 01 2012 | California Institute of Technology | Birefringent polymer brush structures formed by surface initiated ring-opening metathesis polymerization |
| 9284512, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining and producing dibasic esters and acids from natural oil feedstocks |
| 9310304, | May 12 2011 | ANDE CORPORATION | Methods and compositions for rapid multiplex amplification of STR loci |
| 9339805, | Sep 10 1998 | Materia, Inc. | Catalyst complex with carbene ligand |
| 9365487, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining and producing dibasic esters and acids from natural oil feedstocks |
| 9366631, | Apr 04 2007 | ANDE CORPORATION | Integrated systems for the multiplexed amplification and detection of six and greater dye labeled fragments |
| 9382502, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks |
| 9388098, | Oct 09 2012 | Wilmar Trading Pte Ltd | Methods of making high-weight esters, acids, and derivatives thereof |
| 9403854, | Mar 30 2001 | NATIONAL INSTITUTES OF HEALTH NIH , U S DEPT OF HEALTH AND HUMAN SERVICES DHHS , U S GOVERNMENT | Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts |
| 9427731, | Dec 03 2009 | MATERIA, INC | Supported olefin metathesis catalysts |
| 9452568, | Aug 23 2010 | MATERIA, INC | VARTM flow modifications for low viscosity resin systems |
| 9464258, | Oct 12 2009 | Wilmar Trading Pte Ltd | Diene-selective hydrogenation of metathesis derived olefins and unsaturated esters |
| 9469827, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining natural oil feedstocks |
| 9481627, | Dec 22 2011 | Wilmar Trading Pte Ltd | Methods for suppressing isomerization of olefin metathesis products |
| 9494519, | Apr 04 2007 | ANDE CORPORATION | Methods for rapid multiplexed amplification of target nucleic acids |
| 9527982, | Dec 19 2012 | MATERIA, INC | Storage stable adhesion promoter compositions for cyclic olefin resin compositions |
| 9550985, | Jun 15 2009 | ANDE CORPORATION | Methods for forensic DNA quantitation |
| 9598531, | Feb 27 2013 | MATERIA, INC | Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts |
| 9663440, | Apr 09 2013 | MATERIA, INC | Cross metathesis of poly-branched poly-olefins |
| 9663459, | Apr 09 2013 | MATERIA, INC | Preparation of surfactants via cross-metathesis |
| 9708251, | Apr 24 2012 | Stepan Company | Unsaturated fatty alcohol alkoxylates from natural oil metathesis |
| 9732282, | Oct 12 2009 | Wilmar Trading Pte Ltd | Methods of refining natural oil feedstocks |
| 9751975, | Jul 03 2013 | MATERIA, INC | Liquid molding compositions |
| 9758445, | Apr 09 2013 | MATERIA, INC | Preparation of surfactants via cross-metathesis |
| 9758543, | Mar 14 2013 | Wilmar Trading Pte Ltd | Alkenyl glycosides and their preparation |
| 9777245, | Jan 30 2015 | Trent University | Methods of fractionating metathesized triacylglycerol polyols and uses thereof |
| 9796889, | Feb 05 1999 | Materia, Inc. | Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces |
| 9803046, | Mar 15 2013 | MATERIA, INC | In-mold coating of ROMP polymers |
| 9889449, | Apr 04 2007 | ANDE CORPORATION | Integrated systems for the multiplexed amplification and detection of six and greater dye labeled fragments |
| 9890239, | Sep 04 2013 | California Institute of Technology | Functionalized linear and cyclic polyolefins |
| RE38676, | Jul 31 1998 | California Institute of Technology | Thermally initiated polymerization of olefins using ruthenium or osmium vinylidene complexes |
| Patent | Priority | Assignee | Title |
| 4883851, | Jul 25 1988 | California Institute of Technology | Ring opening metathesis polymerization of strained cyclic ethers |
| 4945135, | Jul 25 1988 | California Institute of Technology | Ring opening metathesis polymerization of strained cyclic ethers |
| 4945141, | Jul 25 1988 | California Institute of Technology | Ring opening metathesis polymerization of strained cyclic ethers |
| 4945144, | Jul 25 1988 | California Institute of Technology | Ring opening methathesis polymerization of strained cyclic ethers |
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